Herbicidal compositions containing chlorinated aryl esters of chlorinated aliphatic monocarboxylic acids



Patented Apr. 6, 1954 TENT OFFICE UNITED STATE ACIDS Luther L.Baumgartner, Hastings-on-Hudson,

N. Y., assignor to The B. F. Goodrich Company, New York, N. Y., acorporation of New York No Drawing. Application April 1 1, 1952, SerialNo. 282,268

(El. FL-2.3)

8 Claims.

This invention relates to herbicidal compositions and more specificallypertains to herbicidal compositions containing as an essential activeingredient, a polychloroaryl ester of a chlorinated 2. penta-, hexa-, orheptachlorotolyl ester, a tri-, tetra--, penta-, hexa-, hepta, octa-, ornonachloroxylyl ester, a tetrato heptachloro naphthyi ester; as Weil asany of the cholorethylphenyl aliphatic nionocarhoxylic acid. 5 esters,chloroethyltolyl esters and chloropropyl- In my co ding applicationSerial No. 147,754, phenyl esters which contain 3 or more chlorine March4-, 1950,now U. $.Patent No. 2,59%,278, atoms attached to nuclear carbonatoms of the the herbicidal activity of compositions containbenzenering. The acid portion of these active ing a polychloroaryl ester of analipha"c monoingredients can be derived from the lower alicarhoxylicacid is disclosed. This app cation is phatic acids such as formic,acetic, propionic, a continuation-in-part of above copcnding hutyricacids or may be derived from such fatty l plication. acids as stearicacid and palmitic acid. The acid I have discovered that whenpolychloroaryl portion of these active ingredients may contain esters ofchlorinated aliphatic monocarboxylic one or more chlorine atoms. acidsare mixed with a mineral oil consisting The preferred active ingredientsfor the compredominantly of hydrocarbons containing from position ofthis invention are the pentachloro- 10 to carbon atoms such as keroseneand fuel phenyl esters of chlorinated monocarboxylic acids oils, inconcentrations as low as 0.01% by weight, havii'ig 1 to 6 carbon atomsin the acid residue the resulting compositions are exceedingly eflecofthe ester and from 1 to 9 chlorine atoms tive herbicides. Thesecompositions are especial- 20 attached to the carbon atoms of the acidresidue. ly useful in killing a wide variety of grasses and The activeingredients of the compositions of broad leaf plants including varietieswhich are this invention can be readily and conveniently not controlledeffectively with known herbicides. prepared by methods well known to theart of M era l p0sitions containing the IJ E organic chemical synthesis.For example, they chloroaryl esters in low concentrations of less 35 canhe prepared by reacting a polychlorinated than 1% by weight will killbroad leaf plants phenolic compound with an acyl halide of a and somegrasses while oil compositions containchlorinated monocarboxylic acid.The ester is g t e po ychloroaryl esters in higher concenformed throughthe splitting out of hydrogen trations of 1% to 10% by weight can beemployed chloride. Thus, when pentachlorophenol is, for to eradicateplant life of all kinds which is usually l eacted with phosgene, theproduct refollnd in unpaved d w ys, Clay tennis courts, sulting from thesplitting out of H01 is pentah ghway berms, vacant lots, drainageditches, chlorophenyl chloroforniate, one of the preferred barn 10175,alQll-g fence rows, in meadows a active ingredients. Other methods ofpreparing Plant life killed y Such compositions the polyhaloaryl estersof chlorinated monocarincludes species from such major families of theboxylic acids are W611 known to the art. plant kingdom as Gramineaesolanaceaeg As representative compounds of the preferred ciferae andLegunnnosaand includes speclfically class of active ingrefliems theremay be such i pestsuas for example Wlld aster 9 tioned pentachlorophenylchloroformate; penta- Johnson grass, Wild onion, pepper weed, annual hih- 9 tetla" pentablue grass, Dallas grass, smut grass, carpet grass,Pr0p1onater pemachlorophenyl mono" nut grass, burweed, ragweed,plantain, bindweed, tetra", penta" and heptaichlorf) lambsquarter oxalisfoxtail, and shepherws butyrates; pentachlorophenyl mono-, d1-, tr1-,purse 4, tetra-, penta-, heXa-, hepta-, octa-, nona-chloro- Thepolychloroaryl esters of chlorinated ali- Valera-fies; and the 011101derivatives of Penta phatic monocarboxylic acids utilized as active r phnyl p n h k Wh r n ingredients in this invention contain three or two,three, etc, up to all of the hydrogens oi the more nuclear attachedchlorine atoms per benaliphatic group of the acid portion of thesecomzene ring in the aryl group of the ester. When pounds are replaced bychlorine atoms. the aryl group of the ester contains allzyl sub- Themineral oil used as the carrier in the stituents, one or more of thehydrogens oi the herbicidal compositions described herein may be alkylgroup may also be replaced by chlorine ny O l Consisting PTEdOmiIIHIItIYf hydrocar atoms. Thus for example the ester can be a bo s, preferablyparaffin hydrocarbons 8011mm? tri-, tetraor pentachlorophenyl ester; atetra-, ing 10 to 20 carbon atoms. Such hydrocarbons generally possess aboiling point above 150 C. and a Saybolt viscosity below 200 seconds.Examples of such oils are kerosene, light parafiin base oil, diesel fueloils, Bunker C fuel oil, and other similar hydrocarbon mixtures whetheror not derived from petroleum. In general, the lighter petroleumfractions and especially kerosene are preferably employed in preparingspray compositions for use in temperate climates while the heavierhigher molecular weight petroleum oils such as the diesel fuel oils arebest suited for formulations to be used in the hotter climates.

Compositions consisting entirely of the polychloroaryl esters ofchlorinated aliphatic monocarboxylic acids in a concentration between0.01% and by weight dissolved or dispersed in the carrier oil may besprayed on plants to produce the herbicidal effect. If desired, however,the polychloroaryl esters can be first dissolved in a small amount ofthe oil and then the oil solution dispersed in water with the aid of awetting or dispersing agent to produce an oil-inwater emulsioncontaining from 0.01% to 10% by weight of the polychloroaryl ester andan oil content of from 1% to 100% of that of the water, and theresulting emulsion sprayed on plant life. In either event I have foundthat the application of the compositions in amounts such a to provide aslittle as 1 to pounds of the active ingredient per acre of sprayed areais sufficient to kill a great variety of undesirable weeds and grassesalthough, of course, lower rates of application of from 0.25 to 1.0pound per acre or higher rates of application up to 50 pounds per acreof the active ingredient may be employed in some instances.

Suitable dispersing or wetting agents for the preparation ofoil-in-water emulsion include those typified by the following generalclassifications: Sodium and potassium salts of fatty acids known as softand hard soaps; salts of disproportionated abietic acid known as rosinsoaps; salts of hydroxyaldehyde acids present in seaweed known as alginsoaps; alkali-casein compositions; water-soluble lignin sulfonate salts;long-chain alcohols usually containing 10 to 18 carbon atoms;water-soluble salts of sulfated fatty alcohols containing 10 to 18carbon atoms; water-soluble salts of sulfated fatty acid amides;water-soluble esters of sulfated fatty acids; water-soluble alkylsulfonates having 10 to 18 carbon atoms in the alkyl group;water-soluble aryl sulfonates; water-soluble alkyl aryl sulfonates;watersoluble aralkyl sulfonates; water soluble sorbitan mono-laurate,-pa1mitate, -stearate, and -oleate; quaternary ammonium alkyl halides;fatty acids saponified with amines and amino alcohols; and others.Dispersing or wetting agents of the above classes are sold under varioustrade names. Such products are sometimes pure compounds but generallyare a mixture of compound of the same class with some substance as afiller. When one or more of these dispersing agents are employed toprepare the herbicidal compositions described above, it usually it willbe necessary to use only from about 0.1% to about 5% by weight of thedispersing or wetting agent depending on the efiiciency of thedispersing or wetting agent and the quantity of oil to be emulsified.

The following specific examples illustrate the herbicidal properties ofthe compositions containing polychloroaryl esters of chlorinatedmono-carboxylic acids as the essential activ ingradient.

4 EXAMPLE I Herbicidal compositions containing various amounts ofpentachlorophenyl monoand trichloro acetates dissolved in insecticidegrade kerosene were employed in the form of spray against plantsrepresentative of the various plant families to which numerous commonweed varieties belong. A composition containing 0.1% of thesepentachlorophenyl esters dissolved in kerosene gave a complete kill ofradish, oats, beans, squash, cabbage and tomato plants.

The following are field tests made on numerous weeds growing undernatural conditions.

EXAMPLE II A large area of ground containing a freshly prepared seed bedwas layed out in plots 4 feet by 5.5 feet. Five of these plots weresprayed at the rate of 5 pounds of pentachlorophenyl monochloroacetateper acre. The spray composition contained one pound of this ester foreach twelve gallons of kerosene, about 1.3% by weight. Five other plotswere sprayed at the same rate with a kerosene solution containing 1.3%by weight of pentachlorophenyl trichloroacetate. Five plots were leftuntreated as check plots. These treatments were carried out just as thefirst weed seedlings were breaking ground. The plots were leftuncultivated for eight weeks. At the end of this period all weeds werecut off at ground level and the green weed weights for each test wereaccumulated. The total weight of weed growth for each test and for thecheck plots is tabulated below in Table I.

Table I \t tt on; Chemical of weeds grams Untreated 25, 259Pentachlorophenyl Monochloroacetate 3, 682 PentaclilorophenylTrichloroacetate 2, 770

EXAMPLE III Pentaohlorophenyl Pentachloroplienyl Plant Vanetymonochloroacctate tricliloroacetete 1 germinated No germination.

The activity of specific polychlorphenyl esters of chlorinated aliphaticmonocarboxylic acids has been illustrated in the above specificexamples, but any of the other specific members of the preferred estershereinbefore named will possess substantially the same activity asherbicides. The other members of the preferred group can be used againstweed growth with substantially the same results as indicated in thespecific examples.

Although I have disclosed specific examples of my invention, I do notdesire or intend to limit myself solely thereto for as hitherto stated,the precise proportions of the ingredients used can be varied withoutdeparting from the spirit and scope of the invention as defined in theappended claims.

I claim:

1. A herbicidal composition which comprises as the essential activeingredient 0.01% to by weight of a polychloroaryl ester of a chlorinatedaliphatic monocarboxylic acid, said acid having from 1 to 6 carbon atomsand said polychloroaryl portion of the ester containing at least 3chlorine atoms in the aryl nucleus and, as a carrier therefor, a mineraloil consisting predominantly of hydrocarbons containing 10 to 20 carbonatoms.

2. A herbicidal composition which comprises as the essential activeingredient 0.01% to 10% by Weight of a pentachlorophenyl ester of achlorinated aliphatic monocarboxylic acid, said acid having from 1 to 6carbon atoms and, as a carrier therefor, a mineral oil consistingpredominantly of hydrocarbons containing 10 to 20 carbon atoms.

3. A herbicidal composition which comprises as the essential activeingredient 0.01% to 10% by weight of pentachlorophenylmonochloroacetate, and a carrier therefor, a mineral oil consistingpredominantly of hydrocarbons containing 10 to 20 carbon atoms.

4. A herbicidal composition which comprises as the essential activeingredient 0.01% to 10% by weight of pentachlorophenyl trichloroacetateand, as a carrier therefor, a mineral oil consisting predominantly ofhydrocarbons containing from 10 to 20 carbon atoms.

5. The method of killing plant life which comprises applying to theplant life a composition containing a polychloroaryl ester of achlorinated aliphatic monocar-boxylic acid, said acid having from 1 to 6carbon atoms and said polychloroaryl portion of the ester containing atleast 3 chlorine atoms in the aryl nucleus, said ester being applied ina quantity sufiicient to destroy the growth of undesirable plants.

6. The method of killing plant life which comprises applying to theplant life a composition containing a pentachlorophenyl ester of achlorinated aliphatic monocarboxylic acid, said acid having from 1 to 6carbon atoms, said ester being applied in a quantity sul'licient to killundesirable plant life.

7. The method of killing plant life which comprises applying to theplant life a composition containing pentachlorophenyl monochloroacetatein a quantity sufficient to kill undesirable plant life.

8. The method of killing plant life which comprises applying to theplant life a composition containing pentachlorophenyl trichloroacetatein a quantity sufiicient to kill undesirable plant life.

References Cited in the file of this patent UNITED STATES PATENTS NumberName Date 2,188,734 Carswell Jan. 30, 1940 2,282,732 Lean May 12, 19422,390,941 Jones Dec. 11, 1945 2,393,086 Bousquet Jan. 15, 1946 2,550,049Eaker Apr. 24, 1951 OTHER REFERENCES "Agricultural Chemicals," June1951, page 113.

1. A HERBICIDAL COMPOSITION WHICH COMPRISES AS THE ESSENTIAL ACTIVEINGREDIENT 0.01% TO 10% BY WEIGHT OF A POLYCHLOROARYL ESTER OF ACHLORINATED ALIPHATIC MONOCARBOXYLIC ACID, SAID ACID HAVING FROM 1 TO 6CARBON ATOMS AND SAID POLYCHLOROARYL PORTION OF THE ESTER CONTAINING ATLEAST 3 CHLORINE ATOMS IN THE ARYL NUCLEUS AND, AS A CARRIER THEREFOR, AMINERAL OIL CONSISTING PREDOMINANTLY OF HYDROCARBONS CONTAINING 10 TO 20CARBON ATOMS.